Hydrocarbons obtained by destructive distillation of gilsonite and products made therefrom



United States Patent 3,003,944 HYDROCARBONS OBTAINED BY DESTRUCTIVE DISTILLATION OF GILSONITE AND PRODUCTS MADE THEREFROM Nathan W. Davis, 3474 S. 23rd St., Salt Lake City, Utah No Drawing. Filed Aug. 15, 1956, Ser. No. 604,085 6 Claims. (Cl. 208-22) This invention relates to hydrocarbons obtained by destructive distillation of Gilsonite and to products made from the distillates.

It is an object of this invention to destructively distill Gilsonite and to obtain therefrom various fractions each of which are separate and distinct insofar as they have diflerent physical and chemical properties.

It is a further object of this invention to use one or more of these fractions to obtain an inseoticidal'composition.

It is a still further object of this invention to use one or more of these fractions in compounding a paint composition.

A still further object of this invention is to use one of these distilled fractions in producing an elastomeric product.

Gilsonite is a black, brittle, lustrous mineral consisting of hydrocarbons, chiefly found in the southwestern section of the United States, principally in Utah and Colorado.

DESTRUCT IV E DISTILLATION OF GlLSONITE In a steel still directly heated by means of electric resistance units is placed 50 pounds of Gilsonite M.P. 320- 350 F. This still is connected to a water cooled condenser and the following fractions obtained at the temperature indicated. For the purpose of further reference in this specification, these fractions have been given the following numbers.

Table of Gilsonite distillates using a 320 F. melt point Gilsonite. The following distillates are obtainable:

. Specific Temperature, 13. No. Color Gravity at 70 F.

1 0.61 2 0.73 3 1.72 4 1.71 5 0.053 6 1.31 7 0.63 8 0.93 0 1.12 10 1.19 11 2.11 12 0.74 13 0.87 14 0.89 15 0.79 16 0.52 17 0.90 18 0.67 19 2.69 20 0.054 21 0.093 22 0.94 23 00011 24 0.005 25 0.95 26 0.17 27 0.19 28 1.03 29 0.039 30 0.73 31 0.92 32 0.53 33 V 0.72 31 2.007 35 o 2.09 36 grey black dust, when cool,

remaining in retort. Weight 120 grams to on. inch.

More fractions are obtainable but they are not part of thisinvention.

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Example I A carbon silicate acid is obtained from the 16 fraction by treating as follows:

In a retort that will stand 600 pounds pressure, place- 1 gal. distillate, fraction 16 12 oz. xylene (dimethylbenzene) I 2 oz. triethanolamine (trihydroxytriethylamine) 6 oz. silicon mix (finely ground silicon dioxide 100 mesh) Heat to 250 F. maintaining a pressure of 30 pounds per square inch with continual agitation for one hour.

The retort is then allowed to cool, maintaining the agitation, and when cool, 1 gallon of distilled water is added. This is then distilled and three fractions taken at 230- 240 F., 260270 F. and 310-3l5 F., using a water cooled condenser. The last fraction, that is, the one'boiling at 3l0-3l5 F. is a fluid brownish liquid having a specific gravity of .24 at 70 F., and is then diluted with mineral spirits solvent in the ratio of 1 part distillate to 80 parts solvent. The following solvents have also proven r satisfactory; Stoddart Solvents manufactured by the Standard Oil Company and turpentine. This material has the following formula tion as follows:

Mix in a heated retort with agitation- 1 gal. of #6 fraction (an oily brown, black materialhaving a specific gravity of 1.31 at 70 F.)

r 7 oz. triethanolarnine (trihydroxytriethylamine) 1 lb. silicon mix (finely ground silicon dioxide 100 mesh) 20 oz. xylene (dimethylbenzene) Mix and heat under pressure to 300 F. maintaining a pressure of 20 lbs. per square inch with continual agitation for one hour. Cool and add 1 gal. of distilled water and 1 pt. turpentine. Heat with agitation to 256 F. and distill. An oily distillate having a specific gravity of .63 at 70 F. is obtained. This is a very toxic material and is used in the preparation of insecticides referred to below. This is heretofore referred to as the Z6 material. This material has the following formula:

4H 4CO OH (2Si O2H O Example lI.-Paint A black colloidal non-toxic paint for waterproofing and rust-proofing metal, wood, concrete, etc., .which is resistant to heat, acid and'alkali and moisture can be applied by brushing, spraying or dipping is prepared 'as follows:

Mix and heat in an open vessel- 20 gal. petroleum solvent, such as mineral spirits or xylene 10 gal. boiled linseed oil 10 gal. turpentine, Wood distilled or gum spirits of turpentine.

After heating to F. slowly add lbs. pulverized -200 mesh Gilsonite, a pigment melting at 320-350 F. This mixture is then heated to 150 F., then slowly.

' add 4 gals. of varnish (PT 358 National Lead Company),

1 gal. Petronate 8 or 9, Sonneborn Sons Inc, New York, wetting agent.

2 qts. of a mixture of 1 part lead, 1 part cobalt and 2 parts manganese drier 1 pt. of the penetrating oil not diluted, obtained as outlined above (Z16).

This mixture is heated until the mixture reaches 200 F., continuously mixing for 15 minutes and then allowed to cool. It is drawn oif and sealed in containers. This produces approximately 55 gals. of paint.

Example IIl.-Aluminum paint An aluminum paint, slightly toxic, which is resistant to heat, acid and alkali, as Well as moisture, can be applied by spraying, brushing or dipping, is prepared as follows:

Mix in an open agitator- Mix thoroughly until all of the aluminum pigment is suspended, then draw off and seal in containers.

Example lV.Insecticides The following composition is prepared by mixing in an ordinary agitator:

10 lbs. wheat bran (vehicle) 1 pt. corn syrup (bait) 2 lbs. Gilsonite Z6 (poison) 2 oz. arsenic trioxide (optional), (poison) 2 oz. benzaldehyde (attractant).

This insecticide is especially effective on earwigs, cockroaches and silver fish.

Example V.Insecticides The following composition is prepared by mixing, in an ordinary agitator.

Mix together with continuous agitation-' This is particularly eifective for termites, ants, spiders, and related insects.

Schwars Inc. of

Example Vl.Elastomer This process is adapted to the use of any paraflinic hydrocarbon, such as Gilsonite, elaterite (commonly known as Wurtzalite), Sunnyside hydrocarbons, Rozel asphalt, and also bituminous coal- If bituminous coal is used as the basic material, the first step is slightly varied from the first step applicable when another hydrocarbonis used as the basic material.

4 STEPS IN THE PROCESS STEP NO. 1

(A) For hydrocarbons other than bituminous c0al.-If a solid hydrocarbon other than coal is used as the base material, the hydrocarbon should be powdered. The first mass consists of 27 pounds or any multiple thereof, and based upon a 27 pound quantity, the materials are used in the following ratios:

20 pounds of any paratfinic hydrocarbon other than coal, such as powdered Gilsonite, elaterite (Wurtzalite), Sunnyside hydrocarbons, etc. or Rozel asphalt or other semi-liquid hydrocarbon.

7 pounds of raw linseed oil, or hydrogenated cottonseed oil or any other acid base vegetable oil.

27 pounds This mass as combined is mixed thoroughly until smooth, at normal room temperature.

(B) If bituminous. coal is used as the base material, the first step is as follows, using a mass of 27 pounds or any multiple thereof:

18 pounds of powdered bituminous coal 1.5 pounds of Z16 oil product from Gilsonite as described above in Example I .5 pound of. an oil produced from a solid or semisolid hydrocarbon at a temperature of 490 F. This is the 24 fraction shown previously 7 pounds of raw linseed oil, or any substitute having same reaction and same chemical properties 27 pounds These oils are processed by distillation by heating solids ortsgml-solid hydrocarbons to the temperatures F. as indica e This mass ascombined is mixed thoroughly until smooth, at normal room temperature.

STEP NO. 2

Add to the foregoing base mass as compounded in Step No. 1,,one pound of an oily wax, preferably a substance known as Altawax (or any other oily wax having the same chemical properties and reactions); A description of the process for making Altawax is indicated hereinafter. This wax should be added by mixing it with the base material described in Step No. 1.

STEP NO. 3

Add 1 /2 pounds of a sulfonated product obtained by treating out No. 2 from the distillation of Gilsonite as described above, which boils within the range of 330- 334 F. with sulfuric acid and then add 10% furfural and 5% oleic acid to of the sulfonated product. This is then distilled and a cut distilling at 340 F. to 590 F. The residue is the Altawax referred to above.

STEP NO.

Add one-half pound of furfural which will aid polymerization and also one pound of zinc sulphate which will act as an accelerator of polymerization.

In lieu of zinc sulphate, at least one, of any number of other accelerators may be used to produce the same result, some of which are produced commercially under specified'trade-names, such as: Santocure, Resinex, Silicon, Lumanall, Sulfurdioxide, Ethyleneglycol, Diethyleneglycol, Cresylic Acid, Naphthenic Acid, Sodium sulfonate, Santicizer 141, Peracetic Acid, Elastex 50 B, Carbonex, Bordol, Glycerine, or Oxalic Acid. Various other chemicals or commercial substances may be used which produce the same results.

STEP NO. 5

When all of the substances indicated in Steps No. l, 2, 3 and: 4 have been combined, regardless of which sub stance is first added to the mixed mass of Step N0. 1, whether material describedin Steps No. 2, 3 or 4, the-aggregate of all of these substances should be mixed as herein indicated. vTo accelerate Step thoroughly for approximately one hour at ordinary room pounded substances should be mixed at a moderate speed.

The compounded substances should continue to be mixed at such speed for approximately 6 hours at 200 F. from the time when such temperature is first reached.

STEP NO. '7 The temperature is then gradually increased to 350 F.

with an increase of pressure to 50 pounds, the mixing continuing during this increase in temperature. This mixing process at 50 pou'n'ds'pressure and at 350 F. temperature. continues for abou't'64 hours, unless the time is reduced by additional catalyst or booster in Step No. 4,

No. 7 and to reduce the timefrom 64 hours normally required in Step No. 7, any one or more of the catalysts or accelerators indicated in Step No. 4' may be added tothe zinc sulphate in such quantity as the type of final product may be desired. The extent of reduction in time depends upon the combination and quantity of the accelerators used, however at a slight sacrifice of quality.

STEP NO. 8

The'temperature is then slowly decreased to 250 F. over a period of about 3 hours, during which time the mixing process continues. 1

STEP No. 9

Two pounds of water and one pound of potassium sulfate for a plasticizer, are then added to the mass while the mixing process continues.

STEP NO. 10

The temperature remains at 250 F. while the pressure is increased to 60 pounds by the addition of the water as indicated in Step No. 9. This pressure and this temperature are maintained for about 3 hours while the mixing continues.

STEP NO. 11

The pressure and temperature are then reduced slowly until pressure is entirely released and reduced to zero, and the temperature is reduced to 100 F., while mixing continues.

STEP NO. 12

At this stage 2 pounds of sulphur (which should be at least 90% pure, if possible) should be added to the mass, unless the base material is Rozel asphalt in which event sulphur is not added. There should also be added at this stage of the processing 5 pounds of calcium oxide. These ingredients should be mixed into the mass for about 8 hours at a temperature of about 100 F in an open container under sunlight or ultra-violet rays or other light which produces the same general reaction as sunlight.

STEP NO. 13

The mixing process is then retarded until the mass becomes rubbery and appears somewhat dry. This period should normally occupy about 4 hours.

STEP NO. 14

The processed mass is then removed from the autoclave or other suitable mixing machine which has pressure and heating facilities, and then cured by sunlight or artificial light having similar reaction power. The length of this phase of the process depends upon intensity of light and humidity. Sufiicient moisture must be in the atmosphere to facilitate the curing process.

STEP NO. 15

The cured mass is then ready for use. The material is also in condition for introduction of any rubber extenders or fillers, if desired, to give the elastomer aditferent degree of resiliency, or in order to reduce elasticity.

Example VIL-Ore reduction process This process is adapted to'a separation of complex mineral ores after the raw ore has been crushed and ground to the customary mesh common in conventional means of ore separation. The process 'is adap t-able'to' all rial, ferrous and no'nferrous miner als.

sTE si THE. PROCESS,-

" -s TEP No.'1.

The complex ore as it comes from'th e' bal-l mill or other grinding device, at the required mesh is placed into anagitated heat'edtank for conditioning ,where' the ore material is mixed with warm water to a specific gravity types of complex minerals including radioactive mate- "of .60. Sulfuric acid is then mixed with the material in an amount equal try 1% of the lime content of the ore material while in the process of raising the temperature of the slurry to 200 F. Said temperature should not be I obtained however until after completion of the second step. i t STEP-NO. 2

'Duringithe process described above in Step No. 1, when the lime has quit foaming introduce into the slurry the material previously described in this invention as Z16, in the amount equivalent to A of 1%" of the sul- STEP NO. 4

Now introduce sodium bicarbonate into tank No. 2 in an amount by weight equivalent to twice the number of pounds of sulfuric acid by weight which has been pre viously added, then empty t-ank No. 1 into tank No. 2 'and' slowly agitate.

STEP N0. 5

Then add potassium iodine in an amount equivalent of 2% of the sodium previously added.

STEP NO. 6

Then add and mix into the slurry aluminum nitrate in an amount equivalent of 1% of the potassium iodine previously used. The agitation is now discontinued and the material allowed to settle. A scum forms on the top which is skimmed off and introduced into a separate tank No. 3 containing the same amount of sodium sulfate as there was potassium iodine used previously. Here the scum or material skimmed oif settles and the precipitant is drawn off into evaporating tanks. This is the radioactive material.

STEP NO. 7

If the ore headings contain carbon, use nitric acid in place of sulfuric acid in the preceding steps.

STEP no. a V

The aforesaid steps permit the separation of various ores in the precipitant material contained in tank No. 2 or the soda tank as described in Step No. 4. The various ore particles are free and independent of each other and can be concentrated by conventional methods such as tabling or flotation.

Many minor changes could be made in the above process as described in this application. All such changes come within the scope of this invention. The important microscopic scams or contact points between the various kinds of ore particles'which arecommonlytound united together inniost ore material.

What is claimed is: V v l. A method 'ofprepa'ring abrownish black oil having same andseparating that fraction'which distills between 355 and 360 F.

2. A method of preparing areddish brown liquid having a specific gravity of 0.52 at 70 E, which comprises, introducing into a still,-powdered Gilsonite having a melting point of 320 to 350 F. and fractionall-y distilling the same and-separating that fraction which distills between 430 and 438 F.

3. A product obtained by adding to 1 gallon of the distillate boiling between 430 and 438 F., obtained by the destructive distillation of Gilsonite, 12 ounces of xylene, 2 ounces triethylolarnine and 6 ounces of silicon dioxide, heating under pressure and cooling, adding distilled water and then fractionally distilling the same, and

removing that fraction boiling between 310 and 315 F. 4. A product obtained by adding to 1 gallon of the distillate boiling between 355 and 360 F., obtained by the destructive distillation of Gilsonite, 20 ounces of xylene, 7 ounces triethylolamine and 1 pound of silicon dioxide, heating under pressure to 300 F. and cooling, adding 1 gallon of distilled water and 1 pint of turpentine "and'then distilling the same, and removing that fraction boilingabove'256" F.

A brownish black liquid having a specific gravity of 0.52at 70 R, which is recovered from the destructive distillation of Gil'son'ite, having a melting point range of 320 Fgto 350 F., said fraction being separated at 430 F. to 438 F.

6. A brownish black liquid having a specific gravity r of 1.31 at 70- F. which is 'recovered as a fraction from the destructive distillation of Gilsonitehaving amelting point within the range of 320 F. to 350 F., said fraction being separated at 355 F. to 360 F.

References Cited in the file ofthis patent UNITED STATES PATENTS 1,105,102 Robinson July 28,.1914 1,573,764 Forrest Feb. 16, 1926 1,573,765 1 Forrest Feb: 16, 1926 1,612,672 Vivas; '-'Dec; 28, 1926 1,813,575 Janecke- July 7, 1931 1,940,725 Morrell Dec. 26, 1933 1,954,866 Eglotf Apr. 17, 1934 1,972,944 Morrell Sept. 11,1934 2,285,646 Clocker June 9, 1942 2,344,189 Waldie Mar. 14,1944 2,574,971 Heltzer Nov; '13, 1951 2,580,048 Shmidl Dec. 25, 1951 2,619,446 Andersen Nov. 25, 1952 2,635,978 Massengale Apr. 21, 1953 2,661,331 Howard Dec. 1, 1953 2,719,116 Brown 'Sept.'27; 1955 2,722,512 Crandall Nov. 1, 1955 2,727,054 'Wright Dec. 13, 1955 2,742,372 Colvin Apr. 17, 1956 2,752,381 Peppel June'26, 1956 2,758,126 Goldschrnidt Aug. 7;1956 2,846,361 Mekler Aug. 5, 1958 OTHER REFERENCES Abraham: Asphalts and Allied Substances, 5th ed., vol. 1, 1945, page 253, D: Van Nostrand Co., Inc., New York.

Chem. and Eng. News, vol. 34, July 23, 1956, page 3546. 

5. A BROWNISH BLACK LIQUID HAVING A SPECIFIC GRAVITY OF 0.52 AT 70*F., WHICH IS RECOVERED FROM THE DESTRUCTIVE DISTILLATION OF GILSONITE, HAVING A MELTING POINT RANGE OF 320*F. TO 350*F., SAID FRACTION BEING SEPARATED AT 430*F. TO 438*F. 